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WO1998015584A1 - Copolymeres sequences methacrylate-alkylene-methacrylate - Google Patents

Copolymeres sequences methacrylate-alkylene-methacrylate Download PDF

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Publication number
WO1998015584A1
WO1998015584A1 PCT/GB1997/002764 GB9702764W WO9815584A1 WO 1998015584 A1 WO1998015584 A1 WO 1998015584A1 GB 9702764 W GB9702764 W GB 9702764W WO 9815584 A1 WO9815584 A1 WO 9815584A1
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WO
WIPO (PCT)
Prior art keywords
block
methacrylate
gma
mam
copolymer
Prior art date
Application number
PCT/GB1997/002764
Other languages
English (en)
Inventor
Jianming Yu
Noel Overbergh
John Michael Hudson
Phillip James Hammond
Original Assignee
N.V. Raychem S.A.
Raychem Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by N.V. Raychem S.A., Raychem Limited filed Critical N.V. Raychem S.A.
Publication of WO1998015584A1 publication Critical patent/WO1998015584A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type

Definitions

  • This invention relates to new methacrylate-alkylene-methacrylate (MAM) tri- block or multi-block (preferably penta-block) copolymers.
  • MAM methacrylate-alkylene-methacrylate
  • MAM block copolymers having alkyl methacrylate end blocks, and gels made therefrom, are described in our co-pending International Patent Application No PCT/GB96/01381 (RK509).
  • the new block copolymers according to the present invention have properties not contemplated by that earlier development.
  • the present invention provides a rnethacrylate-alkylene-methacrylate (MAM) triblock or multi-block (preferably penta-block) copolymer of the general structure
  • GM represents a glycidyl methacrylate (GMA) homo- or co-polymer end block
  • E represents one or more optional intermediate blocks of alkyl methacrylate homo- or copolymer or styrene homo- or co-polymer
  • A represents a hydrogenated or unhydrogenated polyalkylene block.
  • the polyglycidylmethacrylate end blocks provide the new MAM copolymers with reactive capabilities not previously available, which may be used for cross-linking or grafting reactions in subsequent use of the new materials.
  • One preferred form of the new MAM copolymers has the triblock copolymer structure GM-A-GM.
  • the intermediate block E is an alkyl methacrylate (M'), preferably methylmethacrylate (MMA), homopolymer block, the MAM copolymer having the structure GM-M'-A-M'-GM.
  • M' block may be a methacrylate copolymer mono-block (that is, a single block of random or other copolymer including the methacrylate units, as distinct from a di-block copolymer) of two or more alkylmethacrylates, or a copolymer mono-block of at least one alkylmethacrylate and another monomer other than a glycidyl methacrylate.
  • the intermediate block E is a styrene (S) homopolymer block, the MAM copolymer having the structure GM-S-A-S- GM.
  • S styrene
  • styrene is understood to include lower alkyl derivatives, notably alpha-methyl styrene, although unsubstituted styrene is preferred.
  • Copolymer mono-blocks of styrene with .another monomer, for example butadiene may be useful as alternatives to the preferred styrene homopolymer blocks.
  • the intermediate block E comprises two different M' blocks (M' 1 and M'2), or an M' block and a styrene block, between the glycidyl methacrylate end blocks GM and the alkylene mid-block A, as illustrated by the structures GM-M'2-M' 1-A-M' l-M'2-GM and GM-M'-S-A-S-M'-GM.
  • M' block could be either a homopolymer block or a copolymer mono-block.
  • GM may be a co-polymer mono- block comprising glycidyl methacrylate and another monomer, preferably an alkyl methacrylate, especially methyl methacrylate (MM A).
  • the preferred polyalkylene blocks A comprise polyisoprene, polybutadiene (PBD), and especially their hydrogenated forms poly(ethylene/propylene), poly(ethylene butylene), and copolymer mixtures thereof.
  • the number average molecular weight Mn of the triblock copolymers for some purposes is preferably within the range 40,000 - 300,000, the methacrylate blocks preferably having Mn within the range 6000 - 70,000, and the alkylene mid-blocks preferably having Mn within the range 30,000 - 160,000. However, these or other molecular weights will be selected to suit the desired end use of the polymers, for example for making gels.
  • the invention includes synthesis of an MAM copolymer as hereinbefore described, comprising (i) polymerisation of an alkylene monomer (preferably butadiene or isoprene) in a substantially apolar solvent (preferably cyclohexane and/or toluene), preferably with addition of a more polar solvent (preferably diethyl ether), to form a difunctional living polyalkylene block, followed by (ii) anionic polymerisation, in the presence of that polyalkylene block, of glycidyl methacrylate at a polymerisation temperature lower than -40 C, preferably lower than -60°C.
  • a substantially apolar solvent preferably cyclohexane and/or toluene
  • a more polar solvent preferably diethyl ether
  • intermediate blocks (E) When intermediate blocks (E) are to be included, the synthesis will include, between steps (i) and (ii), an intermediate step (iii) comprising anionic polymerisation of an alkyl (preferably methyl) methacrylate or styrene to form the intermediate block E. Step (iii) may be repeated sequentially with different monomers when two or more intermediate blocks E are desired. All steps may use mixtures of monomers to give random copolymer blocks.
  • an intermediate step (iii) comprising anionic polymerisation of an alkyl (preferably methyl) methacrylate or styrene to form the intermediate block E.
  • Step (iii) may be repeated sequentially with different monomers when two or more intermediate blocks E are desired. All steps may use mixtures of monomers to give random copolymer blocks.
  • the anionic polymerisation is effected in the presence of a polar solvent, preferably comprising tetrahydrofuran and/or diethyl ether, preferably in a mixture with substantially apolar solvent, preferably toluene and/or cyclohexane.
  • a polar solvent preferably comprising tetrahydrofuran and/or diethyl ether, preferably in a mixture with substantially apolar solvent, preferably toluene and/or cyclohexane.
  • the new block copolymers of the MAM type have been successfully synthesised by using the di-adduct of tert-butyllithium (t-BuLi) to meta-diisopropenylbenzene (m-DIB) as a difunctional initiator.
  • the alkylene midblock A has been synthesised in a cyclohexane/diethylether (100/6, v/v) mixture at room temperature, whereas the methacrylate outer blocks have been synthesised in a mixture of cyclohexane/diethylether/THF (100/6/150, v/v/v) at -78°C.
  • Block copolymers of a very narrow molecular weight distribution (1.10) have been analysed by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and tensile testing. These materials are phase-separated and can exhibit tensile strength up to 22 MPa together with very high elongation at break (1500%).
  • DSC differential scanning calorimetry
  • TEM transmission electron microscopy
  • tensile testing These materials are phase-separated and can exhibit tensile strength up to 22 MPa together with very high elongation at break (1500%).
  • GMA and MMA were first refluxed over CaH 2 under a nitrogen atmosphere, then distilled under reduced pressure and stored under nitrogen at - 20 C. Just before polymerisation, GMA was added at -78 C to a 50/50 (v/v) mixture of diisobutyl aluminium hydride (DIBAH: 0.1N in toluene) and triethylaluminium (TEA: 0.1 N in toluene), whereas MMA was added at room temperature to a similar TEA solution, until a persistent yellowish green colour was observed in the two cases. These monomers were then distilled under reduced pressure.
  • DIBAH diisobutyl aluminium hydride
  • TEA triethylaluminium
  • LiCl 99.99% purity, Aldrich
  • THF dry THF
  • Cyclohexane and diethylether were dried over CaH 2 for 24h, and THF was refluxed over the deep purple sodium-benzophenone complex. After separation, all these solvents were further distilled from polystyryllithium under reduced pressure just before use.
  • Tert-butyllithium (t-BuLi) (Aldrich, 1.3M in cyclohexane) was diluted with cyclohexane into a 0.2N solution and the final concentration determined by double titration.
  • Meta-diisopropenyl benzene (m-DIB, Aldrich) was first dried over CaH 2 for 24 h and then over fluorenyllithium before use.
  • 1,1- diphenylethylene (DPE, Aldrich) was dried over sec-BuLi and distilled from diphenylmethyllithium before use.
  • Butadiene was dried over n-BuLi.
  • Block co-polymerization of butadiene (BD) and GMA was carried out in a previously flamed glass reactor equipped with a magnetic stirrer under an inert atmosphere. Solvent, initiator and monomers were transferred into the reactor with a syringe and/or stainless steel capillaries.
  • Butadiene was first polymerised in a cyclohexane/diethylether mixture (100/6, v/v) at room temperature over night, using a diadduct of m-DIB and two equivalents of t-BuLi (deep red color) as a difunctional initiator previously prepared in cylcohexane at 50 C for 2 hours.
  • Block copolymers were mixed with lwt% Irganox 1010 (Trade Mark, Ciba-Geigy Corp.) hindered phenol antioxidant, and dissolved in toluene. This solution (8wt%) was poured into a Petri dish and the solvent was allowed to evaporate slowly over 3 to 4 days at room temperature. The resulting films were dried to constant weight in a vacuum oven at 40 C. They were elastomeric, transparent and colourless with a smooth surface.
  • Irganox 1010 Trade Mark, Ciba-Geigy Corp.
  • H NMR Spectra were recorded with a Brucker AM-400 spectrometer, using CDC1 3 as a solvent.
  • Composition of the copolymers was calculated by H NMR from the integration of the signal for the 1,2 units of PBD and the signal at 3.5 ppm for the O-CH 3 group of the MMA units or the signals at 2.64, 2.84, 3.23 ppm for the epoxy-ring protons of the GMA units.
  • DSC Differential scanning calorimetry
  • Tensile measurements were conducted with an Adamel Lhomargy tensile tester. Testing samples (microdumbells) cut from solution cast films were extended at 200 mm min at room temperature. Reported data are the average of three measurements.
  • Block copolymers with PBD as the midblock and GMA homopolymer, or copolymers of GMA and MMA, as the outer blocks were synthesised as follows with the di-adduct of m-DIB and two t-BuLi equivalents as a difunctional initiator.
  • GMA homopolymer as the outer blocks In the aforementioned PCT/GB96/01381, the diadduct of t-BuLi onto m-DIB is used as the initiator for the synthesis of MAM triblock copolymers by sequential addition of butadiene and MMA, respectively.
  • the first problem to be solved was the purification of commercial GMA (Aldrich) contaminated by various impurities: inhibitors, methacrylic acid and epichlorohydrin or glycidol.
  • MMA which can be purified by careful distillation from triethylaluminium (TEA)
  • TEA triethylaluminium
  • Typical SEC traces for both the PBD midblock and the triblock copolymer show a very narrow molecular weight distribution (1.10), which suggests that the polybutadienyl dianions end- capped by DPE quantitatively initiate the GMA polymerisation.
  • the copolymerization yield is quantitative.
  • the typical ⁇ NMR spectrum of a poly(GMA-b-BD-b-GMA) triblock shows: absence of resonance characteristic of the methacrylic unsaturation, in agreement with the GMA polymerisation through the carbon-carbon double bond; the two resonances of the ⁇ -methyl protons of GMA units at 0.94 (syndiotactic triads) and 1.10 ppm (heterotactic triads) allow the PGMA tacticity to be calculated; a large resonance at ca.
  • the final triblock copolymer is soluble in common solvents, such as THF and toluene.
  • common solvents such as THF and toluene.
  • each GMA monomeric unit bears an epoxide, indicating that the methacrylic unsaturation is selectively involved in the anionic polymerisation of GMA, whereas the oxirane substituent is kept unchanged.
  • GMA and MMA copolymers as the outer blocks: The nucleophilicity of most methacrylic esters is similar enough for block and random copolymers of GMA and MMA to be synthesised.
  • Table 1 shows that GMA-MMA-BD-MMA-GMA pentablock (sample B) can be synthesised under the same experimental conditions as above, by the sequential addition of MMA and GMA, respectively, to the polybutadienyl dianions end-capped by DPE. The deep red color of the reaction medium disappears upon the addition of MMA, which indicates a fast initiation of the MMA polymerisation. Thirty minutes later, the second monomer GMA is added.
  • the ⁇ NMR spectrum of this copolymer shows the expected resonances for the methoxy protons of the MMA units at 3.56 ppm and the oxirane protons at 2.64, 2.84 and 2.32 ppm, which confirms the GMA and MMA copolymerization.
  • the chemical composition calculated from this H NMR spectrum is in good agreement with the weight ratio of the monomers added to the reaction medium (Table 1).
  • MMA-BD-MMA (hereafter MBM) triblock copolymer (sample D, Table 1) of a weight composition similar to the previously discussed copolymers (A, B, C) has been similarly synthesised for sake of comparison.
  • DSC Differential Scanning Calorimetry
  • phase morphology was analysed by transmission electron microscopy (TEM) and confirmed the phase separation seen by DSC, the thermoplastic outer block, ie. PGMA (sample A), poly(MMA-b-GMA) (sample B), and poly(MMA-co-GMA) (sample C), forming hard micro-domains dispersed in a continuous rubbery phase.
  • the hard phase appears to be spherical, with an average diameter of ca.l0 ⁇ 15nm for the block copolymers of samples A, B and C.
  • phase separation has also been confirmed by stress-strain measurements, which show a stress-strain behaviour typical of a cross-linked rubber, ie, low initial modulus, high elongation at break and high ultimate tensile strength. This observation is indicative of phase separation and efficiency of the PGMA micro-domains in restricting the flow of the soft polybutadiene segments.
  • Table 2 compares the tensile properties of the block copolymer samples.
  • the MGM copolymer sample D is much harder than the three PGMA based block polymers A, B and C of a comparable outer block content, since the initial modulus of MBM copolymer is ca. ten times higher and the elongation at break is smaller (Table 2).
  • the three copolymers containing PGMA based outer blocks have similar tensile properties. Nevertheless, the pentablock copolymer has somewhat higher initial modulus and ultimate tensile strength, which might be the signature of the PMMA component, known to impart hardness to the triblock D. The permanent set is not very different for all samples. Table 1. Block co-polymers with a central PBD block and GMA (or MMA) based outer blocks.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Copolymères séquencés triblocs glycidyl-méthacrylate - alkylène (de préférence butadiène) - glycidyl-méthacrylate, ayant un caractère réactif potentiellement intéressant. Ces triblocs de méthacrylate époxy-modifiés peuvent être utiles pour fabriquer des gels étendus à l'huile et éventuellement pour d'autres objectifs.
PCT/GB1997/002764 1996-10-10 1997-10-08 Copolymeres sequences methacrylate-alkylene-methacrylate WO1998015584A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9621344.2A GB9621344D0 (en) 1996-10-10 1996-10-10 Methacrylate-alkylene-methacrylate block copolymers
GB9621344.2 1996-10-10

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WO1998015584A1 true WO1998015584A1 (fr) 1998-04-16

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0970979A1 (fr) * 1998-07-03 2000-01-12 Kuraray Co., Ltd. Copolymère à blocs et une composition comprenant ledit copolymère
WO2002094898A3 (fr) * 2001-05-18 2003-11-20 Rhodia Elect & Catalysis Procede de preparation de copolymeres blocs
JP2012229354A (ja) * 2011-04-27 2012-11-22 Hitachi Chemical Co Ltd 両末端にポリグリシジルブロックを有するアクリル樹脂及びその製造方法、それを用いた樹脂組成物
JP2016026264A (ja) * 2015-11-18 2016-02-12 日立化成株式会社 両末端にポリグリシジルブロックを有するアクリル樹脂及びその製造方法、それを用いた樹脂組成物

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0462433A2 (fr) * 1990-05-31 1991-12-27 Himont Incorporated Compositions de polyoléfines pouvant être peintes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0462433A2 (fr) * 1990-05-31 1991-12-27 Himont Incorporated Compositions de polyoléfines pouvant être peintes

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0970979A1 (fr) * 1998-07-03 2000-01-12 Kuraray Co., Ltd. Copolymère à blocs et une composition comprenant ledit copolymère
US6228946B1 (en) 1998-07-03 2001-05-08 Kuraray Co., Ltd. Block copolymer and polymer composition comprising the same
WO2002094898A3 (fr) * 2001-05-18 2003-11-20 Rhodia Elect & Catalysis Procede de preparation de copolymeres blocs
JP2012229354A (ja) * 2011-04-27 2012-11-22 Hitachi Chemical Co Ltd 両末端にポリグリシジルブロックを有するアクリル樹脂及びその製造方法、それを用いた樹脂組成物
JP2016026264A (ja) * 2015-11-18 2016-02-12 日立化成株式会社 両末端にポリグリシジルブロックを有するアクリル樹脂及びその製造方法、それを用いた樹脂組成物

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